Anti-static additives

ABSTRACT

An amino methylenesulfonic acid comprising the reaction product of an amine compound (eg) a substituted succinimide containing free primary or secondary nitrogen atoms or a compound of the formula R 1  NH-CH 2  CH 2  CH 2  NH 2  or RNH 2  wherein R and R 1  have 1 to 25 carbon atoms; a compound of the formula ##STR1## wherein R 2  is a hydrogen or a methyl group and R 3  is a hydrogen or an alkyl group having from about 1 to 7 carbon atoms and sulfur dioxide; which can be alternatively reacted with a polyfunctional crosslinking agent; and mixtures of the amino-methylene sulfonic acid with a nitrogen compound adduct of a maleic anhydride olefin copolymer.

This application is a continuation-in-part of Ser. No. 810,378 filedJun. 27, 1977, now abandoned.

Generation of static electricity on hydrocarbons is very dangerous.Numerous explosions and fires have been caused by static sparksresulting from charges generated on hydrocarbons. Commonly, staticcharges are generated on materials which have low conductivities. Lowconductivities commonly result from the general purity of manyhydrocarbons. Commonly, hydrocarbon fuels are materials which have lowconductivities and are susceptible to static charge generation. Aviationjet fuel, for example, often can have conductivity of less than aboutone picosiemen. A minimum conductivity of fifty picosiemens is generallyconsidered necessary to dissipate the static charges generated on thehydrocarbon.

Static charges are commonly built up during storage and transfer offluid hydrocarbons in metal pipes and containers. If the conductivity ofthe hydrocarbons is high, the static charges dissipate quickly. When theconductivities are low, the static charge dissipates very slowly. Sparksoccur when the static is generated faster than the charge can bedissipated. Once the voltage of the static charge passes a certainlevel, called the "breakdown potential," believed to be about 30,000volts, a spark occurs.

Prior art patents which disclose anti-static compositions are U.S. Pat.Nos. 3,449,097; 3,534,975; 3,578,421; 3,677,724; 3,917,466; and4,029,480.

U.S. Pat. No. 3,844,732 discloses fuel detergents comprising thereaction product of a hydrocarbyl (polybutene) substituted aminecompound having at least 30 carbon atoms, an aldehyde and sulfurdioxide. These compounds are produced by first reducing a polyamine withan olefin having greater than 30 carbon atoms, and then reacting thepolyamine-olefin reaction product with a carbonyl compound and sulfurdioxide. The use of succinic anhydride adducts or the use ofpolyfunctional crosslinking agents are not disclosed. Non-crosslinkedcompounds of this type having large (greater than 30 carbon atoms)hydrocarbon group substituted amines have minimal anti-static activity.

U.S. Pat. No. 3,677,724 discloses anti-static compositions forhydrocarbons containing (1) a maleamic acid of a heteropolymer of maleicacid anhydride and a monoolefin having at least two carbon atoms permolecule and an unsubstituted primary amine containing between about 4and about 30 carbon atoms per molecule, glycine or aniline and (2) analkyl vinyl ether/maleic anhydride copolymer; or the reaction product ofan amine salt of the maleic acid of (1) and an alkyl vinyl ether/maleicanhydride copolymer. Mixtures of these composition and the compositionsdisclosed herein can be advantageously used as anti-static compositions.

The compositions currently in use as anti-static agents often suffer thedisadvantage that some fuels which suffer from static caused ignitionand explosion are not protected adequately by cost-effective amounts ofadditive. Thus prior to the compositions disclosed herein protection ofall fuels of interest required more than one additive. Also manyanti-static agents are produced from expensive chemicals which renderthe use of these agents uneconomical.

Accordingly, there is a need for additives and additive mixtures whichare easily produced and blended having high, cost effective activity ina broad spectrum of fuels suffering from the danger of explosions andfire caused by static discharge. Additives which can be blended fuels inlow concentrations and provide protection from fire and explosion areneeded.

The general object of this invention is to provide new classes ofanti-static additives. Another object of the invention is to provideadditive compositions which have beneficial and cost-effective activityin the broad spectrum of fuels which suffer from the danger of explosioncaused by static discharges. Another object of this invention is toprovide anti-static additives which are aminoethylene sulfonic acid andsynergistic mixtures of aminomethylene sulfuric acids and amine-compoundadducts of maleic anhydride-olefin copolymers which are simple toproduce and are simple to blend into the fuels of interest.

The objects of this invention can be attained with (1) an aminomethylenesulfonic acid type product of the reaction comprising an amine compound(eg) either a substituted succinimide containing free primary orsecondary nitrogen atoms or a compound of the formula RNH₂ or R₁ NHCH₂CH₂ CH₂ NH₂ wherein R and R₁ contain 1 to 25 carbon atoms; a compound ofthe formula ##STR2## wherein R₂ is a hydrogen or a methyl group and R₃is a hydrogen or an alkyl group having from about 1 to 7 carbon atomsand sulfur dioxide; or (2) an aminomethylene sulfonic acid product ofthe reaction comprising crosslinking an amine compound such as asubstituted succinimide containing free primary or secondary nitrogenatoms with a polyfunctional cross-linking agent, and reacting thecrosslinked amine with a compound of the formula ##STR3## wherein R₂ isa hydrogen atom or a methyl group and R₃ is a hydrogen atom or an alkylgroup having about 1 to 7 carbon atoms; or (3) a mixture of about 100parts of the aminomethylene sulfonic acid reaction product and fromabout 1 to 10 parts of adduct of a maleic anhydride olefin copolymer andan amine-compound of the formula ##STR4## where X₁, X₂ and X₃ areindependently a hydrogen atom or a hydrocarbyl group of 1 to 20 carbonatoms. These anti-static agents are relatively stable in the monomericand polymeric form and in mixtures, and have high activities in fuelswhich are susceptible to static discharge problems. Furthermore, themonomeric-type compounds can be used as precursors for thepolymeric-type anti-static compositions and blends. The crosslinking ofthe active aminomethylene sulfonic acid anti-static additive enhancesthe properties of the additives, and the mixtures of the aminomethylenesulfonic acid anti-static additive with a maleic anhydride 1-olefincopolymer amine compound adduct produces a mixture with significantlyenhanced activity.

In one aspect this invention is an aminomethylene sulfonic acid.

In a second aspect this invention is an aminomethylene sulfonic acidwhich is crosslinked.

In a third aspect this invention is a mixture of an aminomethylenesulfonic acid and an amine compound adduct of a maleic anhydride olefincopolymer.

In a fourth aspect this invention is a fuel containing an aminomethylenesulfonic acid anti-static agents or synergistic mixtures of theaminomethylene sulfonic acid and the aminocompound adduct of the maleicanhydride olefin copolymer.

Briefly, the aminomethylene sulfonic acids are produced by reacting anamine compound (eg) a substituted succinimide containing free primary orsecondary nitrogen atoms or a compound of the formula RNH₂ R₁ NHCH₂ CH₂CH₂ NH₂ wherein R and R₁ have 1 to 25 carbon atoms with a carbonylcompound and sulfur dioxide. The compounds of this invention cannot berepresented by an exact structural formulae since each reagent used inthe synthesis can react at different active sites (generally nitrogenatoms) on different molecules.

Amine-compounds which can be used to prepare the aminomethylene sulfonicacids are primary monoamines polyamides, preferably alkylene polyaminesand polyalkylene polyamines. Examples of such amines are primary aminesof the formula R-NH₂ wherein R has 1-25 carbon atoms and is methylamine, ethyl amine, propyl amine, isopropyl amine, butyl amine, t-butylamine, oleyl amine, Pentacosenyl amine, etc., ethylene diamine,2-aminoethyl piperazine, diethylene triamine, di(trimethylene) triamine,dipropylene triamine, triethylene tetraamine, tripropylene tetraamine,tetraethylene pentamine, pentaethylene hexamine, etc. Amines having12-25 carbon atoms and polyamines having 4-6 amine nitrogens arepreferred for maximum antistatic activity in the non-crosslinkedanti-static agents.

Amines having the structure R₁ NH-CH₂ CH₂ CH₂ -NH₂ are sold under thename "Duomeen" which includes "Duomeen CD, T, O, and L-15." These arecommercial nitrogen-containing compounds made by the Armak Company. Thecompounds are made by hydrogenating the adduct produced by the reactionof an amine containing up to 25 carbon atoms, preferably 12-25, andacrylonitrile. The reaction product is a n-monoalkyl-1,3-propylenediamine. For example, "Duomeen CD" is the distilled hydrogenatedcocoamine adduct of acrylonitrile. Cocoamine is a C₁₂₋₁₄ primaryhydrocarbon amine, with small amounts of other primary amines. "DuomeenO" is a hydrogenated adduct of an amine and acrylonitrile, wherein theamine is a primary amine having about 18 carbon atoms and isunsaturated. Duomeen T is the hydrogenated adduct of talloamine andacrylonitrile. Talloamine is a mixture of C₁₈, C₁₆, and C₁₄ hydrocarbonamine. As indicated above Duomeens have the general formula R₁ --NH--CH₂CH₂ CH₂ --NH₂ wherein R has 1-25 carbon atoms.

The preferred adduct of acyclic hydrocarbyl succinic anhydride andpolyamines are based on diethylenetriamine, triethylenetetramine, andtetraethylenepentamine. These polyamines are especially preferred due tothe low cost, high activity of resulting anti-static additive andreactivity of the amino nitrogens. Acyclic hydrocarbyl succinicanhydrides having an aliphatic carbon chain from about 12 to 100 carbonatoms, preferably 12-25, in the hydrocarbon substituent are preferred.The molecular weight of the hydrocarbyl group on the succinic anhydrideis about 180 to about 1200, preferably 180-380 to produce monomericanti-static additive of highest activity.

Hydrocarbyl substituted succinic anhydride can be produced by thereaction of maleic anhydride and a polyalkene in an "ENE" reaction or inthe reaction of a chlorinated polyalkene with succinic anhydride. Thereaction between a straight chain paraffin and maleic anhydride alsoproduces an alkyl succinic anhydride with somewhat lower yields. Thepolyalkene is produced from ethene, propene, butene, or mixturesthereof. These reactions are well known in the art.

The adduct of hydrocarbyl succinic anhydride and polyamine is generallya mixture of imides and amides. The molecular structure of an alkyl oralkenyl succinimide (I) and succinamide (II) is represented by thefollowing formula: ##STR5## wherein R₃ is an alkyl or alkenyl grouphaving 12-100 carbon atoms and R₄ is an alkylene group having 2-4 carbonatoms. Generally, the reaction product of an amine and hydrocarbylsuccinic anhydride will be referred to as a hydrocarbyl succinimide,although lesser amounts of hydrocarbyl succinamide, structure (II), aregenerally present. These compounds are also well known in the art.

The carbonyl compounds which react with sulfur dioxide to form sulfonicacid groups are low molecular weight carbonyl compounds having thestructure ##STR6## wherein R₂ is methyl group or hydrogen atom and R₃ ishydrogen atom or alkyl group from 1 to 7 carbon atoms. Aldehydes arepreferred, particularly acetaldehyde and most particularly formaldehyde,for ease of reactivity. Examples of such carbonyl compounds includeformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,isobutyraldehyde, heptaldehyde, acetone, methylethyl ketone, methylisobutyl ketone, etc.

The aldehydes can be used in the monomeric or polymeric form. Linear andcyclic polyaldehydes are formed by polymerization of aldehydes in thepresence of dilute catalyst. Paraformaldehyde can be formed by theaction of dilute catalyst on formaldehyde resulting in a solid cyclictrimer of formaldehyde, named trioxane or commonly paraformaldehyde.Paraformaldehyde, formaldehyde and trioxane are preferred reagents (R₂and R₃ are both hydrogen) due to the ease of handling, reactivity of thereagents and clarity of the products.

In somewhat greater detail, to produce the non-crosslinkedaminomethylene sulfonic acid type anti-static compound, 0.5 to 1.5 molesof the carbonyl compound are added per mole of amine compound. Themixture is stirred until clear at a temperature about room temperature(10° C.) to about 160° C. Sulfur dioxide is then introduced into themixture. This reaction is also exothermic and preferably the temperatureis maintained at between about room temperature and 160° C. About0.1-2.0 moles of sulfur dioxide is added per mole of amine compound.

Briefly, crosslinked aminomethylene sulfonic acid anti-static agents areproduced by reacting an amine compound with a polyfunctionalcrosslinking agent and then reacting the crosslinked amine with acarbonyl compound and sulfur dioxide, or by reacting the non-crosslinkedaminomethylene sulfonic acid with a polyfunctional crosslinking agent.

Crosslinking agents contain two or more groups which are capable ofreacting with and linking amine compounds. The primary or secondarynitrogen atoms of two amine compound molecules react with apolyfunctional crosslinking agent forming amido, imido, amino andurethane-type links. This crosslinking reaction can be performed priorto, or subsequent to producing the amino methylene sulfonic acid thereaction of the amine compound, the carbonyl compound, and the sulfurdioxide. For example, amine containing primary and secondary nitrogenatoms can react with a crosslinking agent prior to further reaction, orthe aminomethylene sulfonic acid can be crosslinked through the freeamine groups in the molecule. The crosslinking reaction and the reactionof the carbon compound and sulfur dioxide can occur at any primary orsecondary nitrogen atom in the amine, and in this way the crosslinkingagent can form large crosslinked units. The amine compound contains onan average at least two secondary or primary nitrogen atoms, one for thecrosslinking reaction, and one for the methylene sulfonic acid reaction.

Examples of polyfunctional compounds reactive with the amine nitrogensare dicarboxylic acid anhydrides, dicarboxylic acid chlorides,hydrocarbyl diisocyanate, and epihalorohydrin, alkylene dihalides,diepoxides, etc. Dicarboxylic acid chlorides include, oxaloyldichloride, succinoyl dichloride, adipoyl dichloride, and terephthaloyldichloride. Hydrocarbyl diisocyantes include, 1,6-heptane-diisocyanate,1,6-hexane-diisocyanate, 1,4-butane diisocyanate, and 1,2-ethanediisocyanate, benzene diisocyanate, and toluene diisocyanate and othersubstituted aromatic diisocyanates. The ease of reactivity, low cost,and high activity of the resulting anti-static compounds make toluenediisocyanate and 1,6-hexane diisocyanate the preferred crosslinkingagents. When diisocyanate is used as a crosslinking agent the productcan be thought of as a urethane type polymer.

Amine compounds which can be used to prepare the crosslinkedaminoethylene sulfonic acid or an adduct of the succinic anhydride whichcan be used to prepare the crosslinked antistatic agent are diamines,triamines, and polyamines, etc., preferably alkylene polyamines andpolyalkylene polyamines. Examples of such amines are ethylene diamine,2-aminoethyl piperazine, diethylene triamine, di(trimethylene)triamine,dipropylene triamine, triethylene tetraamine, tripropylene tetraamine,tetraethylene pentamine, pentaethylene hexamine, etc. Amines having 4-6amine nitrogens are preferred for the high anti-static activity and easeof reactivity.

A preferred amine compound for the crosslinked aminomethylene sulfonicacid is an adduct of a hydrocarbyl substituted succinic anhydride and anamine or polyamine selected from those discussed above. Polyamines suchas, diethylene triamine, triethylene tetraamine, and tetraethylenepentamine are especially preferred due to the low cost, high activity ofresulting anti-static additive and reactivity of the amino nitrogens.Hydrocarbyl substituted succinic anhydrides used for the monomeric typeadditives have from about 12 to 100 carbon atoms, or preferably about12-40 carbon atoms. The molecular weight of the alkyl or alkenyl groupon the succinic anhydride used to produce polymeric type additive isabout 200 to about 1200, preferably 200-600.

The carbonyl compounds used to make the crosslinked aminomethylenesulfonic acid are the same as those for the noncrosslinkedaminomethylene sulfonic acid.

In somewhat greater detail, the crosslinked aminomethylene sulfonic acidanti-static agents are produced by adding slowly to the amine about 0.5to 1.5 equivalents of the cross-linking agent per equivalent of aminecompound at a temperature about room temperature to 160° C. Preferably,the reaction is quickly brought to completion generally within 1 to 2hours with maximum yield when conducted at a temperature of about 60° C.to 120° C.

At the conclusion of the cross-linking reaction, the mixture is cooled.About 0.1 to 1.5 equivalents of the carbonyl compounds per equivalent ofthe amine is added to the cross-linked amine. The mixture is stirreduntil clear at a temperature of about 40° C. to about 200° C. Sulfurdioxide is then introduced into the mixture. This reaction is exothermicand preferably the temperature is maintained at between about roomtemperature to 160° C. About 0.1-2.0 equivalents of sulfur dioxide isadded per mole of amine compound. Optionally, an excess of sulfurdioxide gas is passed into the reaction.

Alternatively about 0.5 to 1.5 equivalents of the crosslinking agent canbe added to the aminomethylene sulfonic acid per equivalents of aminecompound at a temperature from about room temperature (10° C.) to about160° C. for about 1 to 2 hours.

The solvents useful in this invention are inert to sulfur dioxide,amino-containing compounds, and carbonyl-containing compounds.Hyrocarbon aromatics solvents such as benzene and xylene, etc., andother hydrocarbons such as hexane, petroleum ether and petroleumdistillates are suitable solvents.

The preferred solvents are aromatic compounds. One preferred aromaticsolvent is a C₉ + aromatic solvent. This solvent is a mixture ofhydrocarbons resulting from a refinery stream containing aromaticcompounds containing 9 carbon atoms and greater having a boiling pointfrom about 150° C. (300° F.)-200° C. (390° F.) 95%. This solvent is wellknown to the petroleum industry.

The anti-static amino methylene sulfonic acid type additives can beprepared in batch or continuous processes. In batch processes, thesolvent solution of reactants or the reactants without solvent may beadded to the other reactants in a suitable vessel. In continuousprocessing, two components in solution or solvent can be charged todifferent (countercurrent process) or the same reaction zone, e.g., theupper end of a vertical zone maintained at a suitable temperature. Theproduct commonly is withdrawn from the other end into purification orstorage.

Briefly, an effective anti-static composition can be prepared by forminga composition containing about 1 to 100 parts by weight of anaminomethylene sulfonic acid and about 1 part of an amine compoundadduct of a maleic anhydride olefin copolymer. Suitable maleicanhydride-olefin copolymers are made by reacting approximately equimolaramounts of an 1-olefin and maleic anhydride under conventional freeradical conditions. These polymers and their synthesis are well known.Olefins useful in this invention are alpha-olefins, 1-olefins such asethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-octadecene, 1-eicosene, etc.

Further detail of the production of the maleic anhydride olefincopolymer and the subsequent amine compound adduct are found in U.S.Pat. No. 3,003,858, which is incorporated by reference. The preferredmaleic anhydride olefin copolymer has a molecular weight from about 2000to 8000 preferably 4500-6500 and is made from 1-octadecene and maleicanhydride. This copolymer is preferred for the low cost, high activity,and ease of preparation of the components.

The maleic anhydride-olefin copolymer adduct is formed in the reactionwith amine-compound such as ammonia, primary, secondary or tertiaryamines of the formula ##STR7## wherein X₁, X₂ and X₃ are independentlyhydrogen or straight or branched chain alkyl group with 1 to 29 carbonatoms. Examples of suitable amine-compounds are ammonia, methyl amine,ethyl amine, isopropyl amine, n-butyl amine, dibutyl amine, t-butylamine, octadecyl amine, eicosyl amine, dimethyl amine, diethyl amine,methyl isobutyl amine, ethyl isopropyl amine, dioctadecyl amine,trimethyl amine, triethyl amine, triisoamyl amine, trioctadecyl amine,and trieicosyl amine.

The adduct of the amine-compound and the maleic anhydride olefincopolymer contains amide and possibly some imide linkages with theanhydride function on the polymer. The exact nature of the reactionproduct of the tertiary amine maleic anhydride polymer is unknown,although spectrographic studies show amide type bonding. This reactionis well known in the art. The adduct is formed by dissolving orsuspending the copolymer in a hydrocarbon solvent medium. The solutioncan be heated from about room temperature to reflux temperature, about100° C., and the amine compound is added to the mixture until no furtherreaction continues, about 2 hours. The mixture was cooled, filtered, andis ready for use.

The effective mixtures of the crosslinked aminomethylene sulfonic acidand the amine compound adduct of the maleic anhydride 1-olefin copolymercontains about 1 to 100 parts of the polymeric-type sulfonic acid foreach part of the amine compound maleic anhydride olefin copolymeradduct. These mixtures are advantageously made in a hydrocarbon carrierfluid such as a light fraction, kerosene, lubricating oil, toluene,xylene, C₉ + aromatics, etc.

The aminomethylene sulfonic acid or mixture with the polymer adduct in asolvent can be blended into the fuel of interest in concentration offrom about 0.1 to 10.0 parts of additive per million parts of fuel basedon the neat polymer.

Electrical terms which define conductivity are the siemen and the MHO.The practical units are the picosiemen. One picosiemen is equal to 10⁻¹⁴MHO per centimeter of 10⁻¹⁴ per OHM centimeter. Generally a conductivitygreater than about 50 picosiemen/meter are necessary to dissipate staticelectricity.

A field of specific applicability of the present invention is in theimprovement of organic liquid compositions in the form of petroleumdistillate fuel oils having an initial boiling point from about 75° F.to about 135° F. and an end boiling point from about 250 F. to about1000° F. It should be noted, in this respect, that the term "distillatefuel oils" is not intended to be restricted to straight-run distillatefractions. These distillate fuel oils can be straight-run distillatefuel oils, catalytically or thermally cracked (including hydrocracked)distillate fuel oils, or mixtures of straight-run distillate fuel oils,naphthas and the like, with cracked distillate stocks. Moreover, suchfuel oils can be treated in accordance with well-known commericalmethods, such as acid or caustic treatment, hydrogenation, solventrefining, clay treatment, and the like. Distillate fuels arecharacterized by their relatively low viscosity, pour point and thelike. The principal property which characterizes these contemplatedhydrocarbons, however, is their distillation range. As hereinbeforeindicated, this range will lie between about 75° F. and about 1000° F.Obviously, the distillation rang of each individual fuel oil will covera narrower boiling range, falling nevertheless within theabove-specified limits. Likewise, each fuel oil will boil substantiallycontinuously, throughout its distallation range. Particularlycontemplated among the fuel oils are Nos. 1, 2 and 3 fuel oils, used inheating and diesel fuel oils, gasoline, turbine fuels and the jetcombustion fuels, as previously indicated. The domestic fuel oilsgenerally conform to the specifications set forth in ASTM SpecificationD396-48T. Specifications for diesel fuels are defined in ASTMSpecification D-975-48T. Typical jet fuels are defined in MilitarySpecification MIL-F-56248.

EXAMPLE 1

27.0 grams of "Duomeen T" (0.075 moles) a hydrogenated tallow aminederivative of acrylonitrile, and 2.25 grams of paraformaldehyde (0.075moles) were placed in a 300 ml. three-neck flask with 100 ml. of benzene(tallow amine is a natural amine of about 18 carbon atoms) having thetheoretical structure CH₃ (CH₂)₁₇ --NH--(CH₂)₃ --NH₂. The mixture washeated to a temperature from about 55° C. to about 60° C. and 0.075moles of sulfur dioxide was passed into the liquid in about 30 minutes.34.0 grams of 5W oil was added to the clear mixture and benzene wasremoved from the mixture by heating. The product was approximately 50percent additive, based on the oil.

EXAMPLE 2

27.0 grams of "Duomeen O⃡ (0.075 moles) the hydrogenated adduct ofn-oleyl amine and acrylonitrile having a theoretical structure CH₃(CH₂)₇ CH═CH(CH₂)₈ NH(CH₂)₃ NH₂ and 2.25 grams mole of paraformaldehyde(0.075 moles) were placed in a 300 ml. three-neck flask with 100 ml. ofbenzene. The mixture was heated to a temperature from about 55° C. toabout 60° C. and 0.075 moles of sulfur dioxide was passed into theliquid in about 30 minutes. 34.0 grams of 5W oil was added to the clearmixture and benzene was removed from the mixture by heating. The productwas approximately 50 percent additive, based on the oil.

EXAMPLE 3

5.6 grams of diethylenetriamine and 34.4 grams of polybutenyl succinicanhydride in which the polybutyl group has a molecular weight about 450are placed in 100 ml. of xylene in a round bottom flask with a refluxcondenser and a nitrogen atmosphere. The mixture is heated to reflux for3 hours. The solvent is removed and the adduct is recovered bydistillation up to a temperature of 380° F.

40 grams of the polybutenyl succinimide adduct and 1.53 grams ofparaformaldehyde was placed in a 300 ml. three-neck flask with 100 ml.of benzene. The mixture was heated to a temperature of about 55° C. toabout 60° C. and 0.075 moles of sulfur dioxide passed into the liquid inabout 30 minutes. 34 grams of 5W oil was added to the clear mixture andthe benzene was removed from the mixture. The product was approximately50 percent additive, based on oil.

EXAMPLE 4

6.647 g. triethylenetetramine is treated with 30 grams polybutylsuccinic anhydride (0.04545 mole) in 50 ml. of C₉ + in the same manneras in Example 1 forming a triethylene tetraamine adduct of polybutenylsuccinic anhydride.

One mole equivalent of polybutenyl succinimide adduct and 3 moleequivalents of paraformaldehyde was placed in a 300 ml. three-neck flaskwith 100 ml. of benzene. The mixture was heated to a temperature ofabout 55° C. to about 60° C. and about 1 mole equivalent of sulfurdioxide was passed into the liquid until absorption of the gas ceasesabout 30 minutes. 34 grams of 5W oil was added to the clear mixture andthe benzene was removed from the mixture. The yield of product was about100 percent of theoretical. The product was approximately 50 percentadditive, based on the oil.

EXAMPLE 5

Example 1 was repeated except substituting one mole of oleyl amine andone mole of formaldehyde for the "Duomeen T" and the paraformaldehyde.

EXAMPLE 6

Example 1 was repeated except substituting one mole of "Duomeen L-15"and one mole of formaldehyde for the "Duomeen T" and theparaformaldehyde.

EXAMPLE 7

Example 1 was repeated except substituting one mole of "Duomeen L-15"and one mole of propaldehyde for the "Duomeen T" and theparaformaldehyde.

EXAMPLE 8

Example 1 was repeated except substituting one mole of "Duomeen L-15"and one mole of heptaldehyde for the "Duomeen T" and theparaformaldehyde.

EXAMPLE 9

Example 1 was updated except substituting one mole of "Duomeen O" andone mole of formaldehyde for the "Duomeen T" and the paraformaldehyde.

EXAMPLE 10

Example 1 was repeated except substituting one mole of "Duomeen O" andone mole of propaldehyde for the "Duomeen T" and the paraformaldehyde.

EXAMPLE 11

Example 1 was repeated except substituting one mole of "Duomeen O" andone mole of acetaldehyde for the "Duomeen T" and the paraformaldehyde.

EXAMPLE 12

Example 1 was repeated except substituting one mole of oleyl amine forthe "Duomeen T."

EXAMPLE 13

Example 1 was repeated except substituting one mole of formaldehyde forthe paraformaldehyde.

EXAMPLE 14

Example 1 was repeated except substituting one mole of propaldehyde forthe paraformaldehyde.

EXAMPLE 15

Example 1 was repeated except substituting one mole of heptaldehyde forthe paraformaldehyde.

EXAMPLE 16

Example 1 was repeated except substituting one mole of acetaldehyde forthe paraformaldehyde.

EXAMPLE 17

Example 4 was repeated except substituting one mole equivalent offormaldehyde for the paraformaldehyde.

EXAMPLE 18

Example 3 was repeated except substituting 2 mol equivalent offormaldehyde for the paraformaldehyde.

EXAMPLE 19

Example 3 was repeated except substituting 3 moles of formaldehyde forthe paraformaldehyde.

EXAMPLE 20

Example 3 was repeated except substituting 1 mole of acetaldehyde forthe paraformaldehyde.

EXAMPLE 21

Example 3 was repeated except substituting 2 moles of acetaldehyde forthe paraformaldehyde.

EXAMPLE 22

Example 3 was repeated except substituting 3 moles of acetaldehyde forthe paraformaldehyde.

EXAMPLE 23

Example 3 was repeated except substituting one mole of formaldehyde forthe paraformaldehyde.

EXAMPLE 24

Example 3 was repeated except substituting 1.5 moles of formaldehyde forthe paraformaldehyde.

EXAMPLE 25

Example 3 was repeated except substituting 2.0 moles of formaldehyde forthe paraformaldehyde.

EXAMPLE 26

Example 3 was repeated except substituting 2.5 moles of formaldehyde forthe paraformaldehyde.

EXAMPLE 27

Example 3 was repeated except substituting 3.0 moles of formaldehyde forthe paraformaldehyde.

EXAMPLE 28

30.0 g. of polybutenyl succinic anhydride having a molecular weight ofabout 660 (about 0.045 moles) was added to 6.65 g. oftriethylenetetraamine (about 0.045 moles) in 50 cc. of a C₉ + aromaticsolvent in a flask equipped with a stirrer and a nitrogen stream. Thewater of reaction was removed under a nitrogen stream at a temperatureof 180° C. for 1.5 hours forming a succinimide adduct.

To this adduct was added 7.5 g. of 1,6-hexane diisocyanate (about 0.045moles) dissolved in 50 cc. of C₉ + aromatic solvent at 85° C. Thesolution was heated to a temperature of 120° C. for 2 hours and thencooled to 85° C. and 1.3634 g. of paraformaldehyde (about 0.045 moles)was added. The mixture was stirred at 85° C. until it was clear (about30 minutes). 0.045 moles of SO₂ was introduced at a temperature between85° and 95° C. for 3 hours.

EXAMPLE 29

Example 28 was repeated, except with 30 g. of the polybutyl succinicanhydride, 6.64 g. of triethylenetetramine, 7.91 g. of toluenediisocyanate, 1.365 g. of paraformaldehyde, and 2.6 gm SO₂.

EXAMPLE 30

Example 28 was repeated, except with 20 g. of the polybutenyl succinicanhydride, 0.040 moles molecular weight about 500 was reacted with 5.85g. triethylene tetramine, 6.96 g. of toluene diisocyanate, 1.0 g. ofparaformaldehyde, and 2.6 gm SO₂.

EXAMPLE 31

Example 28 was repeated, except with 20 g. of the polybutenyl succinicahydride, molecular weight about 500 (about 0.04 moles), 5.85 g.triethylenetetramine, 6.728 g. of 1,6-hexane diisocyanate, 1.0 g. offormaldehyde, and 2.6 gm SO₂.

EXAMPLE 32

Example 28 was repeated, except with 20 g. of the polybutenyl succinic(about 0.04 moles) anhydride, molecular weight about 500, 5.62 g.triethylene tetramine, 6.469 g. of 1,6-hexane diisocyanate, 1.155 g. ofparaformaldehyde, and 2.6 gm SO₂.

EXAMPLE 33

Example 28 was repeated, except with 20 g. of the polybutenyl succinicanhydride, (about 0.04 moles) molecular weight about 500, 5.571 g.triethylenetetramine, 6.407 g. of 1,6-hexane diisocyanate, 1.144 g. ofparaformaldehyde, and 2.6 gm SO₂.

EXAMPLE 34

Example 28 was repeated in a series of reactions substituting 20 g. ofpolybutenyl succinic anhydride molecular weight about 500, 5.2 gm oftriethylenetetramine 1,6-hexane diisocyanate, 1.44 g. ofparaformaldehyde, and SO₂ (excess) mole ratio of 1,6-hexane diisocyanateto mole of triethylenetetramine was varied as shown below.

    ______________________________________                                        Mole Ratio 1,6 Hexane Diisocyanate/TETA                                       ______________________________________                                                 a           0.0                                                               b           0.2                                                               C           0.6                                                               d           0.8                                                               e           0.9                                                               f           0.95                                                              g           1.00                                                     ______________________________________                                    

EXAMPLE 35

30.0 g. of polybutenyl succinic anhydride, molecular weight about 660,was added to 5.65 g. of triethylenetetramine in 50 ml. of a C₉ +aromatic solvent and heated to 180° C. for 30 minutes. The solution wascooled to 35° and 100 ml. of solvent was added. 6.394 g. of toluenediisocyanate was added slowly and the solution was heated to 160° C. for2 hours. The solution was cooled to 85° C. and 1.1845 g. ofparaformaldehyde was added. The solution was held at 85° C. and stirreduntil clear, approximately 30 minutes. 2.6 gm SO₂ was sparged throughthe solution for 2.5 hours at 85° C.

EXAMPLE 36

Example 35 was repeated except with 30 g. of polybutenyl succinicanhydride, molecular weight about 500, 5.98 g. of triethylenetetramine,6.055 g. of toluene diisocyanate, 1.228 g. of formaldehyde, and 2.6 gmSO₂.

EXAMPLE 37

Example 35 was repeated except with 30 g. of polybutenyl succinicanhydride, molecular weight about 500, 5.807 g. of triethylenetetramine,6.57 of toluene diisocyanate, 1.192 g. of paraformaldehyde, and 2.6 gmSO₂.

EXAMPLE 38

Example 35 was repeated except with 30.0 gm polybutyl succinicanhydride, molecular weight about 540, 4.875 gm TETA, 5.799 gm TDI, and1.00 g paraformaldehyde.

EXAMPLE 39

Example 35 was repeated except with 22.58 grams of polybutenyl succinicanhydride (0.044M) molecular weight about 512, 5.48 gmtriethylenetetraamine (TETA) (0.037 m), 6.53 toluene diisocyanate (TDI)(0.037 m), 1.125 gm formaldehyde (0.037 m) and 2.40 gm of sulfur dioxide(SO₂ 0.037 m).

EXAMPLE 40

Example 29 was repeated except with 5.81 gm TETA (0.039 m) 6.92 gm TDI(0.040 m), 1.192 gm formaldehyde (0.040 m) and 2.541 gm SO₂ (0.040 m).

EXAMPLE 41

Example 35 was repeated except with 24.91 gm polybutenyl succinicanhydride (molecular weight 564.8) (0.044 m), 5.48 gm TETA (0.037 m),6.53 TDI (0.037 m), 1.125 gm formaldehyde (0.037 m) and 2.39 gm SO₂(0.037 m).

EXAMPLE 42

Example 40 was repeated except with 5.81 gm TETA (0.039 m) 6.92 gm TDI(0.040 m), 1.1920 gm formaldehyde (0.040 m) and 2.541 gm SO₂ (0.040 m).

EXAMPLE 43

Example 35 was repeated except with 24.41 gm polybutenyl succinicanhydride (molecular weight 554.9) (0.044 m), 5.48 gm TETA (0.037 m),6.53 TDI (0.037 m), 1.1253 gm formaldehyde (0.037 m) and 2.40 gm sulfurdioxide (0.037 m).

EXAMPLE 44

Example 42 was repeated except with 5.81 gm TETA (0.040 m) 6.92 gm TDI(0.040 m), 1.1920 gm formaldehyde (0.040 m ) and 2.541 gm SO₂ (0.040 m).

EXAMPLE 45

Example 35 was repeated except with 25.48 gms polybutenyl succinicanhydride (molecular weight 578) (0.044 m), 5.48 gm TETA (0.037 m), 6.53TDI (0.037 m), 1.1253 gm formaldehyde (0.037 m) and 2.4 gm sulfurdioxide (0.037 m).

EXAMPLE 46

Example 44 was repeated except with 5.81 gm TETA (0.04 m) 6.92 gm TDI(0.040 m), 1.1920 gm formaldehyde (0.040 m) and 2.54 gm SO₂ (0.040 m).

EXAMPLE 47

Example 35 was repeated with 30.0 gm polybutenyl succinic anhydride.

EXAMPLE 48

20 gm of maleic anhydride octadecene copolymer, molecular weight about5600 was dissolved in 200 ml of toluene and 10 ml of H₂ O added in a 500ml round bottom flask with a reflux condenser. The emulsion was heatedto 65° C. Anhydrous ammonia gas was heated at reflux for three hoursthen cooled and filtered. More toluene was added to reduce the viscosityof the solution at room temperature. The resulting solution in toluenewas 14.16% by weight product.

EXAMPLE 49

10 gm of a maleic anhydride 1-octadiene copolymer, molecular weight5600, was reacted with 4.17 g n-butyl amine in 200 ml of toluene at 100°C. for two hours in a 500 ml round bottom flask with a reflux condenser,then at reflux for two hours until no water or amine distilled. Theresulting solution was 6.88% by weight product in toluene.

EXAMPLE 50

10 gm of a maleic anhydride 1-octadiene copolymer, molecular weightabout 5600, was dissolved in 150 ml of xylene and heated to 90° C. in a500 ml round bottom flask with a reflux condenser. 7.38 gm dibutyl amine(0.73 m) was added to the solution. The solution was heated at 150° forfour hours.

EXAMPLE 51

10 gm of a maleic anhydride 1-octadiene copolymer, molecular weightabout 5600, was dissolved in 200 ml xylene in a 500 ml round bottomflask. 2.5 gm of isoamyl alcohol and 6.67 triisoamyl amine were added.The solution was heated for eight hours at reflux. The solution wascooled.

                  TABLE 1                                                         ______________________________________                                        Conductivity of Jet Fuel Containing                                           Monomeric-Type Additive                                                                     Concentration (PPM) in JP-4 Jet                                 Product in    Fuel at 20° C. for Activity                              Example No.   of 50 picosiemens/meter                                         ______________________________________                                        1             1.0                                                             2             5.9                                                             3             3.3                                                             4             2.0-3.0                                                         5             13.0                                                            6             6.7                                                             7             4.25                                                            8             3.3                                                             9             5.9                                                             10            8.0                                                             11            2.1                                                             12            13                                                              13            1.0                                                             14            7.0                                                             15            4.3                                                             16            2.3                                                             17            4.0                                                             18            6.0                                                             19            4.0                                                             20            10.0                                                            21            10.0                                                            22            10.0                                                            23            4.0                                                             24            5.1                                                             25            2.0-3.0                                                         26            2.0-3.0                                                         27            2.0-3.0                                                         ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        CONDUCTIVITY OF #2 FUEL CONTAINING                                            POLYMERIC-TYPE ADDITIVE                                                                     Conc                                                            Product in Example                                                                          (PPM)      (picosiemen/meter)                                   ______________________________________                                        28            2          94.6                                                 29            10         103                                                  30            10         49                                                   31            10         100                                                  32            10         155                                                  33            10         168                                                  34a           10         104                                                   b            10         117                                                   c            10         144                                                   d            10         176                                                   e            10         108                                                   f            10         132                                                   g            10         98                                                   35            10         305                                                  36            10         193                                                  37            10         363                                                  38            10         194                                                  ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        Conductivity of #2 Heating Fuel                                               Containing Mixture of Polymeric-Type Additives                                                        Conductivity of                                                               Fuel picosie-                                                                 mens/meter                                            Additive (Conc., ppm base on neat additive)                                                           at 74° F.                                      ______________________________________                                        Base Fuel               21.0                                                  Example 39 (10 ppm)     211.0                                                 Example 40 (10 ppm)     197.0                                                 Example 41 (10 ppm)     224.0                                                 Example 42 (10 ppm)     158.0                                                 Example 43 (10 ppm)     227.0                                                 Example 44 (10 ppm)     210.0                                                 Example 45 (10 ppm)     262.0                                                 Example 46 (10 ppm)     219.0                                                 Example 47 (10 ppm)     175.0                                                 Example 48 (1.0 ppm)    184.0                                                 Example 49 (1.0 ppm)    175.0                                                 Example 50 (1.0 ppm)    33.0                                                  Example 51 (1.0 ppm)    45.0                                                  Example 45 (10 ppm) + Example 48 (1.0 ppm)                                                            894.0                                                 Example 45 (10 ppm) + Example 48 (2.0 ppm)                                                            1216.0                                                Example 45 (1 ppm) + Example 48 (0.1) ppm)                                                            92.0                                                  Example 45 (10 ppm) + Example 49 (1 ppm)                                                              1002.0                                                Example 45 (10 ppm) + Example 49 (2 ppm)                                                              1369.0                                                Example 39 (10 ppm) + Example 48 (1 ppm)                                                              661.0                                                 Example 39 (10 ppm) + Example 48 (2 ppm)                                                              1094.0                                                Example 40 (10 ppm) + Example 48 (1 ppm)                                                              743.0                                                 Example 40 (10 ppm) +  Example 48 (2 ppm)                                                             1142.0                                                Example 39 (10 ppm) + Example 49 (1 ppm)                                                              778.0                                                 Example 39 (10 ppm) + Example 49 (2 ppm)                                                              1216.0                                                Example 40 (10 ppm) + Example 49 (1 ppm)                                                              516.0                                                 Example 40 (10 ppm) + Example 49 (2 ppm)                                                              1251.0                                                Example 41 (10 ppm) + Example 49 (1 ppm)                                                              919.0                                                 Example 41 (10 ppm) + Example 49 (2 ppm)                                                              1263.0                                                Example 42 (10 ppm) + Example 49 (1 ppm)                                                              533.0                                                 Example 42 (10 ppm) + Example 49 (2 ppm)                                                              973.0                                                 Example 41 (10 ppm) + Example 48 (1 ppm)                                                              486.0                                                 Example 41 (10 ppm) + Example 48 (2 ppm)                                                              973.0                                                 Example 42 (10 ppm) + Example 48 (1 ppm)                                                              529.0                                                 Example 42 (10 ppm) + Example 48 (2 ppm)                                                              966.0                                                 Example 43 (10 ppm) + Example 49 (1 ppm)                                                              859.0                                                 Example 43 (10 ppm) + Example 49 (2 ppm)                                                              1340.0                                                Example 44 (10 ppm) + Example 49 (1 ppm)                                                              919.0                                                 Example 44 (10 ppm) + Example 49 (2 ppm)                                                              1313.0                                                Example 43 (10 ppm) + Example 48 (1 ppm)                                                              486.0                                                 Example 43 (10 ppm) + Example 48 (2 ppm)                                                              1103.0                                                Example 44 (10 ppm) + Example 48 (1 ppm)                                                              612.0                                                 Example 44 (10 ppm) + Example 48 (1 ppm)                                                              1059.0                                                Example 46 (10 ppm) + Example 48 (1 ppm)                                                              560.0                                                 Example 46 (10 ppm) + Example 48 (2 ppm)                                                              1251.0                                                Example 46 (10 ppm) + Example 49 (1 ppm)                                                              516.0                                                 Example 46 (10 ppm) + Example 49 (2 ppm)                                                              1288.0                                                Example 47 (10 ppm) + Example 48 (1 ppm)                                                              435.0                                                 Example 47 (10 ppm) + Example 48 (2 ppm)                                                              951.7                                                 Example 47 (10 ppm) + Example 49 (1 ppm)                                                              760.0                                                 Example 47 (10 ppm) + Example 49 (2 ppm)                                                              1042.0                                                ______________________________________                                    

Table I shows the beneficial antistatic activity of the aminomethylenesulfonic acid in some cases as little as 13 ppm provide adequateconductivity. Table II also shows beneficial antistatic activity of thecrosslinked aminomethylene sulfonic acid. The crosslinking increases theactivity of the agent. Table III shows the great increase produced bythe composition comprising the crosslinked antistatic additive and theamine-compound maleic anhydride octadecene copolymer adduct. As littleas 1 ppm of the adduct of Example 49 with 10 ppm of the crosslinkedaminomethylene sulfonic acid Example 45 gives a conductivity of 1002.The conductivity of Example 49 alone is 175 and the conductivity ofExample 45 alone is 262 giving a total expected conductivity of 437.Together the agents more than double the expected value.

Many variations from the examples and illustrations found above arepossible. The examples and illustrations shown are to describe specificcompositions which were prepared. Those skilled in the art will be ableto create many other variations similar to those examples found above.These examples should not be used in determining the scope of thisinvention.

I claim:
 1. A crosslinked aminomethylene sulfonic acid compositioncomprising the reaction product of:A. the reaction product of an amineand about 0.5 to 1.5 equivalents of a polyfunctional crosslinking agentper equivalent of amine and said amine contains at least two primary orsecondary nitrogen atoms, B. about 0.1 to 1.5 equivalents of a carbonylcompound having the formula: ##STR8## wherein R₂ is a hydrogen or methylgroup and R₃ is a hydrogen or an alkyl group having 1 to 7 carbon atomsper equivalent of component A; and C. about 0.1 to 2.0 equivalents ofsulfur dioxide per equivalent of amine component of A.
 2. Thecomposition of claim 1 wherein the polyfunctional crosslinking agent isselected from the group consisting of toluene diisocyanate, 1,6-hexanediisocyanate and benzene diisocyanate.
 3. The composition of claim 1wherein the amine is an adduct of a hydrocarbyl substituted succinicanhydride and a polyamine.
 4. The composition of claim 3 wherein thepolyamine is selected from the group consisting of diethylenetriamine,triethylenetetraamine, and tetraethylenepentamine.
 5. The composition ofclaim 1 wherein R₂ and R₃ of the carbonyl compound are hydrogen.
 6. Afuel containing 0.1 to 10.0 parts of the aminomethylene sulfonic acid ofclaim 1 per million parts of fuel.
 7. The composition of claim 1 whereinthe polyfunctional cross-linking agent comprises a dicarboxylicanhdyride.
 8. The composition of claim 1 wherein the polyfunctionalcross-linking agent comprises a dicarboxylic acid chloride.
 9. Thecomposition of claim 1 wherein the polyfunctional cross-linking agentcomprises a hydrocarbyl diisocyanate.
 10. The composition of claim 1wherein the polyfunctional cross-linking agent comprises an alkanedihalide.
 11. The composition of claim 1 wherein the polyfunctionalcross-linking agent comprises a diepoxide.
 12. The composition of claim1 wherein the polyfunctional cross-linking agent comprises anepihalohydrin.